Thermographic recording material with improved image tone and/or stability upon thermal development

ABSTRACT

A recording material comprising a support and a thermosensitive element containing silver behenate, an organic reducing agent therefor in thermal working relationship therewith and a binder, wherein the silver behenate is not associated with mercury and/or lead ions and when the recording material is irradiated with a copper Kα 1  X-ray source the ratio, normalized to a quantity of silver in the recording material of 1 g per m 2  thereof, of the sum of the peak heights of the X-ray diffraction lines attributable to silver behenate at Bragg angles, 2Θ, of 6.01°, 7.56°, 9.12°, 10.66°, 12.12° and 13.62° to the sum of the peak heights of the X-ray diffraction lines at Bragg angles, 2Θ, of 25.60°, 35.16° and 43.40° of NIST standard 1976, rhombohedral Al 2  O 3 , determined with the same X-ray diffractometer in the same state of adjustment, is greater than 0.85; production processes for particles of substantially light-insensitive organic silver salt comprising silver behenate with these X-ray characteristics in the presence and substantial absence of organic solvent.

This is a divisional of application Ser. No. 08/982,318 filed Dec. 10,1997, U.S. Pat. No. 6,096,486.

This application claims the benefit of U.S. Provisional Application No.60/038,769 filed Feb. 20, 1997.

DESCRIPTION

1. Field of the Invention

The present invention relates to a thermographic recording materialsuitable for thermal development. In particular, it concernsimprovements in the image tone upon imagewise thermal developmentthereof and archivability and light stability of the thermographicprints thereof.

2. Background of the Invention

Thermal imaging or thermography is a recording process wherein imagesare generated by the use of thermal energy.

In direct thermal thermography a visible image pattern is formed byimage-wise heating of a recording material containing matter that bychemical or physical process changes colour or optical density. Suchrecording materials become photothermographic upon incorporating aphotosensitive agent which after exposure to UV, visible or IR light iscapable of catalyzing or participating in a thermographic processbringing about changes in colour or optical density.

Most of the "direct" thermographic recording materials are of thechemical type. On heating to a certain conversion temperature, anirreversible chemical reaction takes place and a coloured image isproduced.

According to U.S. Pat. No. 3,080,254 a typical heat-sensitive(thermographic) copy paper includes in the heat-sensitive layer athermoplastic binder, a water-insoluble silver salt and an appropriateorganic reducing agent. Thermo-sensitive copying paper is used in"front-printing" or "back-printing" using infra-red radiation absorbedand transformed into heat in contacting infra-red light absorbing imageareas of an original as illustrated in FIGS. 1 and 2 of U.S. Pat. No.3,074,809.

GB-A 1,378,734 discloses a process of producing a silver salt of anorganic carboxylic acid, which comprises mixing (a) an aqueous solutionof silver nitrate or a silver complex with (b) a solution of an organiccarboxylic acid in a solvent in which the organic carboxylic acid issoluble, both the silver salt of an organic carboxylic acid and silvernitrate being almost insoluble and with which water is sparinglymiscible, so as to react the organic carboxylic acid with silver ions,the reaction being conducted in the presence of a soluble mercurycompound and/or a soluble lead compound.

EP-A 754 969, published after the priority date of the presentapplication, discloses a process for producing a suspension of particlescontaining a substantially light-insensitive silver salt of an organiccarboxylic acid, comprising simultaneous metered addition of an aqueoussolution or suspension of an organic carboxylic acid or its salt; and anaqueous solution of a silver salt to an aqueous liquid, wherein themetered addition of the aqueous solution or suspension of the organiccarboxylic acid or its salt; and/or the aqueous solution of the silversalt is regulated by the concentration of silver ions or theconcentration of anions of the silver salt in the aqueous liquid.

Research Disclosure number 17029, published in June 1978, in section IIgives a survey of different methods of preparing organic heavy metalsalts. Method 5, for example, describes the preparation of silverbehenate by (a) heating behenic acid in water to a temperature above themelting point of the acid, but below the boiling point of thedispersion, (b) adding an aqueous solution of alkali metal or ammoniumhydroxide, and (c) adding an aqueous solution of silver nitrate.However, in order to obtain a fine emulsion of an organic heavy metalsalt, either the synthesis has to be carried out in an organic solventmedium as disclosed, for example, in U.S. Pat. No. 3,700,458 or in amixture of water and a substantially water insoluble organic solvent asdisclosed, for example, in U.S. Pat. No. 3,960,908 for silvercarboxylates.

The association of silver behenate with mercury or lead ions,particularly mercury ions, as disclosed in GB 1,378,734 isenvironmentally undesirable and infringes governmental regulations.Direct thermal recording materials with silver behenates produced usingthe processes described in RD 17029 upon image-wise heating exhibit abrown image colour which is undesirable for medical images viewed intransmission with a viewing box. This lack of image colour neutralitycan be quantified by spectrophotometric measurements according to ASTMNorm E179-90 in a R(45/0) geometry with evaluation according to ASTMNorm E308-90 to produce the CIELAB a* and b* coordinates. Colourneutrality on the basis of CIELAB-values corresponds to a* and b* valuesof zero, with a negative a*-value indicating a greenish image-tonebecoming greener as a* becomes more negative, a positive a*-valueindicating a reddish image-tone becoming redder as a* becomes morepositive, a negative b*-value indicating a bluish image-tone becomingbluer as b* becomes more negative and a positive b*-value indicating ayellowish image-tone becoming yellower as b* becomes more positive.

OBJECTS OF THE INVENTION

It is therefore an object of the invention to provide a thermographicrecording material, which on imagewise thermal development produces animage with a perceptibly bluer image tone.

It is a further object of the present invention to provide athermographic and photothermographic recording materials whose printsexhibit improved archivability and light stability.

It is a still further object of the present invention to provideproduction processes for substantially light-insensitive organic silversalt comprising silver behenate.

Further objects and advantages of the invention will become apparentfrom the description hereinafter.

SUMMARY OF THE INVENTION

Surprisingly it has been found that thermographic recording materialscomprising a support and a thermosensitive element comprising silverbehenate with a higher crystallinity, an organic reducing agent thereforin thermal working relationship therewith and a binder exhibit aperceptibly bluer image tone upon imagewise thermal development and/orproduces thermographic prints with improved archivability and/orimproved light stability, when silver behenate is present therein with asubstantially increased crystallinity over prior art materials.

The above mentioned object is realised with a recording materialcomprising a support and a thermosensitive element containing silverbehenate, an organic reducing agent therefor in thermal workingrelationship therewith and a binder, wherein the silver behenate is notassociated with mercury and/or lead ions and when the recording materialis irradiated with a copper Kα₁ X-ray source the ratio, normalized to aquantity of silver in the recording material of 1 g per m² thereof, ofthe sum of the peak heights of the X-ray diffraction lines attributableto silver behenate at Bragg angles, 2Θ, of 6.01°, 7.56°, 9.12°, 10.66°,12.12° and 13.62° to the sum of the peak heights of the X-raydiffraction lines at Bragg angles, 2Θ, of 25.60°, 35.16° and 43.40° ofNIST standard 1976, rhombohedral Al₂ O₃. determined with the same X-raydiffractometer in the same state of adjustment, is greater than 0.85.

A recording process is also provided according to the present inventioncomprising the steps of: (i) bringing an outermost layer of the abovedescribed recording material in proximity with a heat source; and (ii)applying heat from the heat source imagewise heating to the recordingmaterial while maintaining proximity to the heat source to produce animage; and (iii) removing the recording material from the heat source.

A production process for particles of substantially light-insensitiveorganic silver salt comprising silver behenate is also providedaccording to the present invention comprising the steps of: i) producinga solution or dispersion, A, comprising an alkali metal or ammonium saltof an organic compound with at least one acidic hydrogen atom comprisingbehenic acid in a mixture of water and an organic solvent at atemperature at which the particles of substantially light-insensitiveorganic silver salt comprising silver behenate do not undergo reduction;and ii) adding a quantity of an aqueous solution, B, of a silver saltcontaining an equal number of silver ions to the alkali or ammonium ionsin the solution or dispersion A; characterized in that the initialmixing number during the addition of the aqueous solution B to thesolution or dispersion A is greater than or equal to 2×10⁻⁴ during theproduction of the particles of substantially light-insensitive organicsilver salt comprising silver behenate, the mixing number being theratio of the molar rate at which the silver salt is supplied to thesolution A in a reactor to the molar rate at which the alkali orammonium salt is circulated in the reactor.

A production process for a dispersion of particles of substantiallylight-insensitive organic silver salt including silver behenate in anaqueous medium is further provided according to the present inventioncomprising the steps of: i) producing an aqueous dispersion of one ormore organic acids including behenic acid and an anionic surfactant; ii)substantially neutralizing the organic acids with aqueous alkali therebyforming organic acid salts including a behenic acid salt; (iii) addingan aqueous solution of a silver salt to completely convert the organicacid salt(s) into their silver salts including silver behenate,characterized in that the anionic surfactant is present in a molar ratiowith respect to organic acid greater than 0.15 and the silver salt isadded at a rate between 0.025 mol/mol organic silver salt.min and 2.25mol/mol organic silver salt.min.

Preferred embodiments of the invention are disclosed in the dependentclaims.

DETAILED DESCRIPTION OF THE INVENTION

In a preferred embodiment of the recording process, according to thepresent invention, the heat source is a thermal head with a thin filmthermal head being particularly preferred.

Thermosensitive Element

The thermosensitive element, according to the present invention,comprises silver behenate, an organic reducing agent therefor in thermalworking relationship therewith and a binder. The element may contain alayer system in which the ingredients may be dispersed in differentlayers, with the proviso that the two ingredients are in reactiveassociation with one another i.e. during the thermal development processthe reducing agent must be present in such a way that it is able todiffuse to the silver behenate so that reduction of silver behenate tosilver can occur giving the desired image-tone.

In a preferred embodiment of the present invention the thermosensitiveelement further comprises a photosensitive species capable upon exposureof forming a species capable of catalyzing reduction of the silverbehenate.

Silver Behenate Characterization

The silver behenate in the recording material, of the present invention,wherein when irradiated with a copper Kα₁ X-ray source the ratio,normalized to a quantity of silver in the recording material of 1 g perm² thereof, of the sum of the peak heights of the X-ray diffractionlines attributable to silver behenate at Bragg angles, 2Θ, of 6.01°,7.56°, 9.12°, 10.66°, 12.12° and 13.62° to the sum of the peak heightsof the X-ray diffraction lines at Bragg angles, 2Θ, of 25.60°, 35.16°and 43.40° of NIST (National Institute of Standards, Gaithersburg, Md.20899-0001, USA) standard 1976, rhombohedral Al₂ O₃, determined with thesame X-ray diffractometer in the same state of adjustment, is greaterthan 0.85. In a preferred embodiment of the present invention, thenormalized ratio, as defined above, is greater than 1.0 and in aparticularly preferred embodiment is greater than 1.2.

The normalized ratio is obtained by determining X-ray diffractionspectra on sheets of a particular recording material and of the NISTstandard 1976 cut to fit the sample holder of the X-ray diffractometerused, subtracting the background using standard techniques, determiningthe peak heights of the diffraction peaks, determining for the sample ofrecording material the sum of the peak heights, K_(material), of the XRDlines attributable to silver behenate at Bragg angles, 2Θ, of 6.01°,7.56°, 9.12°, 10.66°, 12.12° and 13.62°, determining for the sample ofNIST standard 1976 the sum of the peak heights, K₁₉₇₆, of the X-raydiffraction lines at Bragg angles, 2Θ, of 25.60°, 35.16° and 43.40°,calculating the ratio of K_(material) /K₁₉₇₆ for the recording material,determining the concentration of silver C_(Ag) present in the recordingmaterial in grams per square meter of material and finally normalizingthe ratio K_(material) /K₁₉₇₆ with C_(Ag) to give the normalized ratioK_(material) /(K₁₉₇₆ ×C_(Ag)), which is referred to in the detaileddescription of the present invention as the crystallinity of silverbehenate.

The concentration of silver present in the recording material can bedetermined by any known technique e.g. non-destructive methods such asX-ray fluorescence and destructive methods such as dissolution of thesilver salt followed by standard volumetric techniques for thedetermination of silver, such as described in R. Belcher and A. J.Nutten, Quantitative Inorganic Analysis, 2nd Edition, Butterworths,London (1960), pages 201-219.

A standard test was used to assess the image tone of thermographicrecording materials comprising silver behenate of the present invention.This consisted of first coating a subbed 175 μm thick polyethyleneterephthalate support with a solvent dispersion comprising: silverbehenate (AgB), 400% by weight of relative to AgB of polyvinylbutyral,50 mol % relative to AgB of ethyl 3,4-dihydroxybenzoate, 15 mol %relative to AgB of benzo[e][1,3]oxazine-2,4-dione, 5 mol % relative toAgB of 7-(ethylcarbonato)benzo[e][1,3]oxazine-2,4-dione, 0.9 wt % ofsilicone oil relative to AgB, 5 mol % relative to AgB oftetrachlorophthalic anhydride, 21.98 mol % relative to AgB of adipicacid and 10 mol % relative to AgB of benzotriazole to a coating weightof AgB of about 5 g/m². After drying for 1 hour at 50° C., thethermographic recording material was tempered for 7 days at 45° C.Thermal printing was carried out with the print head separated from thethermosensitive layer by a separable 5 μm thick polyethyleneterephthalate ribbon coated successively with a subbing layer,heat-resistant layer and a slipping layer (anti-friction layer) and aprinter equipped with a thin film thermal head with a resolution of 300dpi and operated with a line time of 19 ms (the line time being the timeneeded for printing one line). During the line time the print headreceived constant power. The average printing power, being the totalamount of electrical input energy during one line time divided by theline time and by the surface area of the heat-generating resistors was1.5 mJ/dot. The image tone was assessed both by visual inspection and onthe basis of the L*, a* and b* CIELAB-values of the image as a functionof the optical density of the image determined with a MACBETH™ TR924densitometer. The L*, a* and b* CIELAB-values were determined byspectrophotometric measurements according to ASTM Norm E179-90 in aR(45/0) geometry with evaluation according to ASTM Norm E308-90. Thevalue of b* at the minimum in the dependence of b* upon image density ofless than -2.0 was found to correspond with an image with a blue tonecompared with images with a brown tone for minima with higher b* values.

Compounds for Promoting Silver Behenate Crystallinity

Non-halide ion containing phosphonium compounds have been found topromote the crystallinity of silver behenate. Preferred non-halide ioncontaining phosphonium compounds for promoting silver behenatecrystallinity according to the present invention are:

PC01=(2-methoxyethyl)triphenylphosphonium toluenesulphonate

PC02=ethyltriphenylphosphonium toluenesulphonate

PC03=(2-triphenylphosphonium)ethyltriphenylphosphonium benzenesulphonate

Silver Behenate

The silver behenate of the present invention is not associated withmercury and/or lead ions. This means that mercury/and or silver ions arenot intentionally added at any point during the preparation process andtherefore are not intentionally associated with the silver behenate inthe recording material of the present invention.

Silver Behenate Preparation in Solvent/Water Media

Any known synthesis technique and any known dispersion technique can beused to produce the silver behenate of the present invention with theprovision that the silver behenate in the thermographic recordingmaterial of the present invention fulfils the above criteria.

In a preferred embodiment of the recording material of the presentinvention, the silver behenate is present in the thermosensitive elementas particles of substantially light-insensitive organic silver saltcomprising the silver behenate.

The above described production process for particles of substantiallylight-insensitive organic silver salt comprising silver behenate ischaracterized in that the mixing number during the addition of theaqueous solution B to the solution or dispersion A is greater than orequal to 2×10⁻⁴ during the production of the particles of substantiallylight-insensitive organic silver salt comprising silver behenate, themixing number being the ratio of the molar rate at which the silver saltis supplied to the solution A in a reactor to the molar rate at whichthe alkali or ammonium salt is circulated in the reactor. The mixingnumber can be expressed as follows: ##EQU1## C_(B) =concentration ofsolution B in moles/dm³ M₀ =initial quantity of alkali metal or ammoniumsalt of an organic compound with at least one acidic hydrogen atomcomprising behenic acid present in solution A in moles

V₀ =volume of solution A in the reactor in dm³

G_(F) =pumping number of the stirrer in the reactor

n=stirring rate in rotations/minute

D=stirrer diameter in dm

t=time in minutes

The pumping number of the stirrer in a reactor is the ratio of stirrerpumping rate to the product of the stirrer diameter cubed and thestirring rate (n×D³) and is dependent on a variety of factors, such asthe ratio of stirrer to reactor diameter, the off-bottom clearance ratioof the stirrer and the Reynolds number of the stirrer, see for exampleA. Bakker and L. E. Gates, Chemical Engineering Progress pages 25 to 34(December 1995) and Nagata, "Mixing Principles and Applications", J.Wiley & Sons, New York (1975), pages 136-139.

The mathematical nature of the above function for the mixing number issuch that the mixing number will always increase as the preparation ofthe particles of organic silver salt comprising silver behenateproceeds.

In a preferred production process, according to the present invention,the solution or dispersion A has a molar concentration of alkali metalor ammonium salt of organic compound with at least one acidic hydrogenatom comprising behenic acid in the mixture of water and an organicsolvent greater than 0.022.

In another preferred production process, according to the presentinvention, the organic solvent is present at between 20 and 80% byweight of the mixture and preferably between 35 and 65% by weight of themixture. In further preferred production process the organic solvent is2-butanone.

Surprisingly it has been found from scanning electron micrographs ofdispersions of particles of organic silver salt comprising silverbehenate and from transition electron micrographs of thin slices ofthermosensitive layers coated from dispersions of particles of organicsilver salt comprising silver behenate that the shape of these particlesin general changes from rods to a more globular shape as the mixingnumber is increased and that this change in particle morphology isaccompanied by an increase in the crystallinity, as defined above,provided that the dispersion of these particles of organic silver saltcomprising silver behenate is carried out under similar conditions. In apreferred embodiment of the recording material of the present inventionat least 20% by weight of the particles of organic silver saltcomprising silver behenate is present as globular particles and in aparticularly preferred embodiment of the recording material of thepresent invention at least 40% by weight of the particles of organicsilver salt comprising silver behenate is present as globular particles.

Preparation of Aqueous Dispersions of Silver Behenate-ContainingParticles in the Substantial Absence of Solvent

A production process for a dispersion of particles of substantiallylight-insensitive organic silver salt including silver behenate in anaqueous medium is provided according to the present invention comprisingthe steps of: i) producing an aqueous dispersion of one or more organicacids including behenic acid and a salt of an alkylarylsulfonate; ii)substantially neutralizing the organic acids with aqueous alkali therebyforming organic acid salts including a behenic acid salt; (iii) addingan aqueous solution of a silver salt to completely convert the organicacid salts into their silver salts including silver behenate,characterized in that the anionic surfactant is present in a molar ratiowith respect to organic acid greater than 0.15 and the silver salt isadded at a rate between 0.025 mol/mol organic silver salt.min and 2.25mol/mol organic silver salt.min. In preferred embodiments of theproduction process for a dispersion of particles of substantiallylight-insensitive organic silver salt including silver behenate in anaqueous medium the anionic surfactant is present in a molar ratio withrespect to organic carboxylic acid greater than 0.25 and the silver saltis added at a rate between 0.03 mol/mol organic silver salt.min and 0.7mol/mol organic silver salt.min, with a molar ratio of anionicsurfactant with respect to organic acid greater than 0.3 and a rate ofsilver salt addition of between 0.04 mol/mol organic silver salt.min and0.3 mol/mol organic silver salt.min being particularly preferred.

In a preferred embodiment step (iii) of the production process of thepresent invention is carried out such that part the solution of acidsalts produced in step (ii) of the process is present in the reactionvessel prior to silver salt solution addition and part thereof is addedsimultaneously with the addition of the silver salt solution, with about25 to 50% of the solution of acid salts produced in step (ii) being inthe reaction vessel prior to silver salt addition being particularlypreferred.

In another preferred embodiment of the production process for adispersion of particles of substantially light-insensitive organicsilver salt including silver behenate in an aqueous medium the anionicsurfactant is selected from the group consisting of: alkylsulfonatesalts, alkarylsulfonate salts, aralkylsulfonate salts, arylsulfonatesalts, alkylsulfate salts, aralkylsulfate salts, arylsulfate salts,alkarylsulfate salts and organic carboxylate salts. In a particularlypreferred embodiment of the present invention the anionic surfactant isan alkarylsulfonate salt and in an especially preferred embodiment theanionic surfactant is an alkylbenzene sulfonate salt. Suitable anionicsurfactants for use in the production process for a dispersion ofparticles of substantially light-insensitive organic silver saltincluding silver behenate in an aqueous medium according to the presentinvention are:

Surfactant Nr. 1=MARLON™ A-396, a sodium alkylphenylsulfonate from Huls;

Surfactant Nr. 2=Marlon™ A-53, an alkylphenylsulfonic acid from Hulsneutralized with an alkali hydroxide;

Surfactant Nr. 3=ammonium 4-dodecylbenzene sulfonate;

Surfactant Nr. 4=ULTRAVON™ W, a sodium arylsulfonate from Ciba-Geigy;

Surfactant Nr. 5=ERKANTOL™ BX, a sodium diisopropylnaphthalenesulfonatefrom BAYER;

Surfactant Nr. 6=ALKANOL™ XC, a sodium nonylnaphthalenesulfonate from DUPONT;

Surfactant Nr. 7=HOSTAPUR™, a secondary alkanesulfonate from HOECHST;

Surfactant Nr. 8=MERSOLAT™ H80, a sodium hexadecylsulfonate from Bayer;

Surfactant Nr. 9=HOSTAPAL™ B, a sodium trisalkylphenylpolyethyleneglycol(EO 7-8) sulphate from Hoechst;

Surfactant Nr. 10=TERGITOL™ 4, a sodium1-(2'-ethylbutyl)-4-ethylhexylsulphate from GOLDSCHMIDT;

The above-described production process for a dispersion of particles ofsubstantially light-insensitive organic silver salt including silverbehenate in an aqueous medium the pH used must be sufficiently low toavoid the oxidation of silver ions to silver oxide or silver hydroxidefor which a pH below 10 is usually required, the process temperature ischosen such that it is above the melting point of the organic acid(s)used which in the case of behenic acid means a temperature of about 80to 85° C., must be carried out with stirring, the stirring rate beingdependent upon the size of the stirrer relative to the reaction vessel,the type of stirrer used, avoidance of silver oxide or silver hydroxideformation due to insufficient mixing and avoidance of foaming, and beingusually between 200 and 1000 rpm and a slight excess of an organic acid,for example behenic acid with e.g. 2 mol % excess being preferred.

The size of the silver acid salts particles containing silver behenatecan be varied by varying the rate of silver salt addition, theconcentration of anionic surfactant and the temperature, the equivalentdiameter of the particles increasing with decreasing addition rate,decreasing anionic surfactant concentration and increasing temperature.

In a further preferred embodiment production of the process for adispersion of particles of substantially light-insensitive organicsilver salt including silver behenate in an aqueous medium according tothe present invention the production process also includes a step inwhich the silver organic salt including silver behenate is subject toultrafiltration. The ultrafiltration process removes ionic species andconcentrates the silver behenate dispersion by filtration through acartridge-filter with a pore size sufficiently small to remove the saltproduced upon the formation of the organic silver salt without removingthe silver behenate. Cartridge-filters with 10,000 to 500,000 MW havebeen found to be suitable for this purpose. In order to maintain thestability of the silver behenate dispersion during ultrafiltration it isnecessary to maintain a minimum anionic surfactant concentration, butthe counterion of the anionic surfactant can be changed, should thepresence of the original counterion be undesirable in the thermographicrecording material. For example the sodium ions in Surfactant nr 1 canbe replaced by ammonium ions by washing with an ammonium nitratesolution during the ultrafiltration process and the sodium ionconcentration reduced to below 100 ppm.

Substantially Light-Insensitive Organic Silver Salt Dispersions

Should it be necessary to produce dispersions with particles of organicsilver salt comprising silver behenate with higher crystallinity, asdefined above, it has been found that thermographic recording materials,according to the present invention, can be produced, if dispersionsthereof are produced using dispersion techniques in which the particlesthemselves are subjected to as little damage as possible commensuratewith achieving a satisfactory dispersion quality. The use ofmicrofluidizers, ultrasonic apparatuses, rotor stator mixers etc. havebeen found to be useful in this regard.

Surfactants and Dispersion Agents

Surfactants and dispersants aid the dispersion of ingredient orreactants which are insoluble in the particular dispersion medium. Thethermographic recording materials of the present invention may containone or more surfactants, which may be anionic, non-ionic or cationicsurfactants and/or one or more dispersants.

Suitable dispersants are natural polymeric substances, syntheticpolymeric substances and finely divided powders, for example finelydivided non-metallic inorganic powders such as silica. Suitablehydrophilic natural or synthetic polymeric substances contain one ormore hydroxyl, carboxyl or phosphate groups, e.g. protein-type binderssuch as gelatin, casein, collagen, albumin and modified gelatin;modified cellulose; starch; modified starch; modified sugars; modifieddextrans etc. Examples of suitable hydrophilic synthetic polymericsubstances are polyvinylalcohol; polyvinylpyrrolidone; polyacrylic acid;and polymethacrylic acid and their copolymers.

Reducing Agents

Suitable organic reducing agents for the reduction of the substantiallylight-insensitive organic heavy metal salts are organic compoundscontaining at least one active hydrogen atom linked to O, N or C, suchas is the case with, aromatic di- and trihydroxy compounds;aminophenols; METOL (tradename); p-phenylenediamines; alkoxynaphthols,e.g. 4-methoxy-1-naphthol described in U.S. Pat. No. 3,094,41;pyrazolidin-3-one type reducing agents, e.g. PHENIDONE (tradename);pyrazolin-5-ones; indan-1,3-dione derivatives; hydroxytetrone acids;hydroxytetronimides; hydroxylamine derivatives such as for exampledescribed in U.S. Pat. No. 4,082,901; hydrazine derivatives; andreductones e.g. ascorbic acid; see also U.S. Pat. Nos. 3,074,809,3,080,254, 3,094,417 and 3,887,378.

Among useful aromatic di- and tri-hydroxy compounds having at least twohydroxy groups in ortho- or para-position on the same aromatic nucleus,e.g. benzene nucleus, hydroquinone and substituted hydroquinones,catechol, pyrogallol, gallic acid and gallic acid esters are preferred.Particularly useful are polyhydroxy spirobis-indane compounds.

Among the catechol-type reducing agents, i.e. reducing agents containingat least one benzene nucleus with two hydroxy groups (--OH) inortho-position, the following are preferred: catechol,3-(3,4-dihydroxyphenyl) propionic acid, 1,2-dihydroxybenzoic acid,gallic acid and esters e.g. methyl gallate, ethyl gallate, propylgallate, tannic acid, and 3,4-dihydroxy-benzoic acid esters.Particularly preferred catechol-type reducing agents, are described inEP-B 692 733 and unpublished European Patent Application EP 97202872.4.

Other suitable reducing agents, particularly for photothermographicrecording materials, are sterically hindered phenols, bisphenols andsulfonamidophenols.

Combinations of reducing agents may also be used that on heating becomereactive partners in the reduction of the substantiallylight-insensitive organic silver salt comprising silver behenate. Forexample, combinations of reducing agents with sulfonamidophenols aredescribed in the periodical Research Disclosure, February 1979, item17842, in U.S. Pat. Nos. 4,360,581 and 4,782,004, and in EP-A 423 891and combinations of sterically hindered phenols with sulfonyl hydrazidereducing agents such as disclosed in U.S. Pat. No. 5,464,738; tritylhydrazides and formyl-phenyl-hydrazides such as disclosed in U.S. Pat.No. 5,496,695; trityl hydrazides and formyl-phenyl-hydrazides withdiverse auxiliary reducing agents such as disclosed in U.S. Pat. No.5,545,505, U.S. Pat. No. 5,545,507 and U.S. Pat. No. 5,558,983;acrylonitrile compounds as disclosed in U.S. Pat. No. 5,545,515 and U.S.Pat. No. 5,635,339; and 2-substituted malondialdehyde compounds asdisclosed in U.S. Pat. No. 5,654,130.

Organic reducing metal salts, e.g. stannous stearate, have also beenused in such reducing agent combinations, as disclosed in U.S. Pat. Nos.3,460,946 and 3,547,648. Sterically hindered phenols and bisphenols havethemselves been used in such reducing agent combinations, such asdescribed in U.S. Pat. No. 4,001,026 and U.S. Pat. No. 3,547,648respectively.

The silver image density depends on the coverage of the above definedreducing agent(s) and organic silver salt(s) and has to be preferablysuch that, on heating above 100° C., an optical density of at least 2.5can be obtained. Preferably at least 0.10 moles of reducing agent permole of organic silver salt is used.

Polycarboxylic Acids and Anhydrides Thereof

According to the recording material of the present invention thethermosensitive element may comprise in addition at least onepolycarboxylic acid and/or anhydride thereof in a molar percentage of atleast 20 with respect to all the organic silver salt(s) present and inthermal working relationship therewith. The polycarboxylic acid may bealiphatic (saturated as well as unsaturated aliphatic and alsocycloaliphatic) or an aromatic polycarboxylic acid. These acids may besubstituted e.g. with alkyl, hydroxyl, nitro or halogen. They may beused in anhydride form or partially esterified on the condition that atleast two free carboxylic acids remain or are available in the heatrecording step.

Particularly suitable are saturated aliphatic dicarboxylic acidscontaining at least 4 carbon atoms, e.g.: succinic acid, glutaric acid,adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,nonane-dicarboxylic acid, decane-dicarboxylic acid, undecanedicarboxylicacid.

Suitable unsaturated dicarboxylic acids are: maleic acid, citraconicacid, itaconic acid and aconitic acid. Suitable polycarboxylic acids arecitric acid and derivatives thereof, acetonedicarboxylic acid,iso-citric acid and α-ketoglutaric acid.

Preferred aromatic polycarboxylic acids are ortho-phthalic acid and3-nitro-phthalic acid, tetrachlorophthalic acid, mellitic acid,pyromellitic acid and trimellitic acid and the anhydrides thereof.

Film-Forming Binders of the Thermosensitive Element

The film-forming binder of the thermosensitive element containing thesubstantially light-insensitive organic heavy metal salt may be allkinds of natural, modified natural or synthetic resins or mixtures ofsuch resins, wherein the organic heavy metal salt can be dispersedhomogeneously: e.g. cellulose derivatives such as ethylcellulose,cellulose esters, e.g. cellulose nitrate, carboxymethylcellulose, starchethers, galactomannan, polymers derived from α,β-ethylenicallyunsaturated compounds such as polyvinyl chloride, after chlorinatedpolyvinyl chloride, copolymers of vinyl chloride and vinylidenechloride, copolymers of vinyl chloride and vinyl acetate, polyvinylacetate and partially hydrolyzed polyvinyl acetate, polyvinyl alcohol,polyvinyl acetals that are made from polyvinyl alcohol as startingmaterial in which only a part of the repeating vinyl alcohol units mayhave reacted with an aldehyde, preferably polyvinyl butyral, copolymersof acrylonitrile and acrylamide, polyacrylic acid esters,polymethacrylic acid esters, polystyrene and polyethylene or mixturesthereof.

A particularly suitable polyvinyl butyral containing a minor amount ofvinyl alcohol units is marketed under the trade name BUTVAR™ B79 ofMonsanto USA and provides a good adhesion to paper and properly subbedpolyester supports.

The layer containing the organic silver salt is commonly coated onto asupport in sheet- or web-form from an organic solvent containing thebinder dissolved therein, but may also be applied from an aqueous mediumcontaining a water-dispersible binder and/or a water dispersible binder.

Suitable water-soluble film-forming binders for use in thermographic andphotothermographic recording materials according to the presentinvention are: polyvinyl alcohol, polyacrylamide, polymethacrylamide,polyacrylic acid, polymethacrylic acid, polyvinylpyrrolidone,polyethyleneglycol, proteinaceous binders such as gelatin, modifiedgelatins such as phthaloyl gelatin, polysaccharides, such as starch, gumarabic and dextran and water-soluble cellulose derivatives. A preferredwater-soluble binder for use in the thermographic and photothermographicrecording materials of the present invention is gelatin.

Suitable water-dispersible binders for use in the thermographic andphotothermographic recording materials of the present invention may beany water-insoluble polymer e.g. water-insoluble cellulose derivatives,polyurethanes, polyesters polycarbonates and polymers derived fromα,β-ethylenically unsaturated compounds such as after-chlorinatedpolyvinyl chloride, partially hydrolyzed polyvinyl acetate, polyvinylalcohol, polyvinyl acetals preferably polyvinyl butyral, andhomopolymers and copolymers produced using monomers selected from thegroup consisting of: vinyl chloride, vinylidene chloride, acrylonitrile,acrylamides, methacrylamides. methacrylates, acrylates, methacrylicacid, acrylic acid, vinyl esters, styrenes, dienes and alkenes; ormixtures thereof. It should be noted that there is no clear cuttransition between a polymer dispersion and a polymer solution in thecase of very small polymer particles resulting in the smallest particlesof the polymer being dissolved and those slightly larger being indispersion.

Preferred water-dispersible binders for use according to the presentinvention are water-dispersible film-forming polymers with covalentlybonded ionic groups selected from the group consisting of sulfonate,sulfinate, carboxylate, phosphate, quaternary ammonium, tertiarysulfonium and quaternary phosphonium groups. Further preferredwater-dispersible binders for use according the the present inventionare water-dispersible film-forming polymers with covalently bondedmoieties with one or more acid groups.

Water-dispersible binders with crosslinkable groups, e.g. epoxy groups,aceto-acetoxy groups and crosslinkable double bonds are also preferred.

Preferred water-dispersible binders for use in the thermographic andphotothermographic recording materials of the present invention arepolymer latexes. For use as a latex the dispersible polymer haspreferably some hydrophilic functionality. Polymers with hydrophilicfunctionality for forming an aqueous polymer dispersion (latex) aredescribed e.g. in U.S. Pat. No. 5,006,451, but serve therein for forminga barrier layer preventing unwanted diffusion of vanadium pentoxidepresent as an antistatic agent.

Binder to Organic Silver Salt Ratio

The binder to organic silver salt weight ratio is preferably in therange of 0.2 to 6, and the thickness of the recording layer ispreferably in the range of 5 to 50 μm.

Thermal Solvent

The above mentioned binders or mixtures thereof may be used inconjunction with waxes or "heat solvents" also called "thermal solvents"or "thermosolvents" improving the reaction speed of the redox-reactionat elevated temperature. By the term "heat solvent" in this invention ismeant a non-hydrolyzable organic material which is in solid state in therecording layer at temperatures below 50° C. but becomes a plasticizerfor the recording layer in the heated region and/or liquid solvent forat least one of the redox-reactants, e.g. the reducing agent for theorganic heavy metal salt, at a temperature above 60° C.

Toning Agent

In order to obtain a neutral black image tone in the higher densitiesand neutral grey in the lower densities the recording layer containspreferably in admixture with the organic heavy metal salts and reducingagents a so-called toning agent known from thermography orphotothermography.

Suitable toning agents are the phthalimides and phthalazinones withinthe scope of the general formulae described in U.S. Pat. No. 4,082,901.Further reference is made to the toning agents described in U.S. Pat.Nos. 3,074,809, 3,446,648 and 3,844,797. Other particularly usefultoning agents are the heterocyclic toner compounds of the benzoxazinedione or naphthoxazine dione type as disclosed in GB-P 1,439,478, U.S.Pat. No. 3,951,660 and U.S. Pat. No. 5,599,647. A toner compoundparticularly suited for use in combination with polyhydroxy benzenereducing agents is 3,4-dihydro-2,4-dioxo-1,3,2H-benzoxazine described inU.S. Pat. No. 3,951,660.

Other Additives

The recording layer may contain in addition to the ingredients mentionedabove other additives such as free fatty acids, surface-active agents,antistatic agents, e.g. non-ionic antistatic agents including afluorocarbon group as e.g. in F₃ C(CF₂)₆ CONH(CH₂ CH₂ O)--H, siliconeoil, e.g. BAYSILONE™ Ol A (from BAYER AG, GERMANY), ultraviolet lightabsorbing compounds, white light reflecting and/or ultraviolet radiationreflecting pigments and/or optical brightening agents.

Support

The support for the thermal imaging material according to the presentinvention may be transparent, translucent or opaque, e.g. having a whitelight reflecting aspect and is preferably a thin flexible carrier madee.g. from paper, polyethylene coated paper or transparent resin film,e.g. made of a cellulose ester, e.g. cellulose triacetate,polypropylene, polycarbonate or polyester, e.g. polyethyleneterephthalate. For example, a paper base substrate is present which maycontain white reflecting pigments, optionally also applied in aninterlayer between the recording material and the paper base substrate.

The support may be in sheet, ribbon or web form and subbed if need be toimprove the adherence to the thereon coated thermosensitive recordinglayer. The support may be made of an opacified resin composition, e.g.polyethylene terephthalate opacified by means of pigments and/ormicro-voids and/or coated with an opaque pigment-binder layer, and maybe called synthetic paper, or paperlike film; information about suchsupports can be found in EP's 194 106 and 234 563 and U.S. Pat. Nos.3,944,699, 4,187,113, 4,780,402 and 5,059,579. Should a transparent basebe used, the base may be colourless or coloured, e.g. having a bluecolour.

One or more backing layers may be provided to control physicalproperties such as curl and static.

Outermost Layer

The outermost layer of the recording material may in differentembodiments of the present invention be the outermost layer of thethermosensitive element, a protective layer applied to thethermosensitive element or a layer on the opposite side of the supportto the thermosensitive element.

Protective Layer

According to a preferred embodiment of the recording material, accordingto the present invention, the thermosensitive element is coated with aprotective layer to avoid local deformation of the thermosensitiveelement and to improve resistance against abrasion.

The protective layer preferably comprises a binder, which may besolvent-soluble, solvent-dispersible, water-soluble orwater-dispersible. Among the solvent-soluble binders polycarbonates asdescribed in EP-A 614 769 are particularly preferred. However,water-soluble or water-dispersible binders are preferred for theprotective layer, as coating can be performed from an aqueouscomposition and mixing of the protective layer with the immediateunderlayer can be avoided by using a solvent-soluble orsolvent-dispersible binder in the immediate underlayer.

A protective layer according to the present invention may comprise inaddition a thermomeltable particle optionally with a lubricant presenton top of the protective layer as described in WO 94/11199. In apreferred embodiment at least one solid lubricant having a melting pointbelow 150° C. and at least one liquid lubricant in a binder is present,wherein at least one of the lubricants is a phosphoric acid derivative.

Water-Soluble or Water-Dispersible Binder for Outermost Layer

According to an embodiment of the present invention the outermost layerof the recording material may comprise a water-soluble binder, awater-dispersible binder or a mixture of a water-soluble and awater-soluble binder. Suitable water-soluble binders for the outermostlayer are, for example, gelatin, polyvinylalcohol, cellulose derivativesor other polysaccharides, hydroxyethylcellulose, hydroxypropylcelluloseetc., with hardenable binders being preferred and polyvinylalcohol beingparticularly preferred. Suitable water-dispersible binders are polymericlatexes.

Crosslinking Agents for Outermost Layer

The outermost layer according to the present invention may becrosslinked. Crosslinking can be achieved by using crosslinking agentssuch as described in WO 95/12495 for protective layers, e.g.tetra-alkoxysilanes, polyisocyanates, zirconates, titanates, melamineresins etc., with tetraalkoxysilanes such as tetramethylorthosilicateand tetraethylorthosilicate being preferred.

Matting Agents for Outermost Layer

The outermost layer of the recording material according to the presentinvention may comprise a matting agent. Suitable matting agents aredescribed in WO 94/11198 and include e.g. talc particles and optionallyprotrude from the outermost layer.

Lubricants for Outermost Layer

Solid or liquid lubricants or combinations thereof are suitable forimproving the slip characteristics of the recording materials accordingto the present invention.

Solid lubricants which can be used according to the present inventionare polyolefin waxes, ester waxes, polyolefin-polyether blockcopolymers, amide waxes, polyglycols, fatty acids, fatty alcohols,natural waxes and solid phosphoric acid derivatives. Preferred solidlubricants are thermomeltable particles such as those described in WO94/11199.

Liquid lubricants which can be used according to the present inventionaccording to the present invention are fatty acid esters such asglycerine trioleate, sorbitan monooleate and sorbitan trioleate,silicone oil derivatives and phosphoric acid derivatives.

Photosensitive Species

A preferred photosensitive species capable upon exposure of formingspecies capable of catalyzing reduction of the silver behenate of thepresent invention is silver halide.

The photosensitive silver halide used in the present invention may beemployed in a range of 0.1 to 100 mol percent; preferably, from 0.2 to80 mol percent; particularly preferably from 0.3 to 50 mol percent;especially preferably from 0.5 to 35 mol %; and especially from 1 to 12mol % of substantially light-insensitive organic silver salt.

The silver halide may be any photosensitive silver halide such as silverbromide, silver iodide, silver chloride, silver bromoiodide, silverchlorobromoiodide, silver chlorobromide etc.

The silver halide may be in any form which is photosensitive including,but not limited to, cubic, orthorhombic, tabular, tetrahedral, octagonaletc. and may have epitaxial growth of crystals thereon.

The silver halide used in the present invention may be employed withoutmodification. However, it may be chemically sensitized with a chemicalsensitizing agent such as a compound containing sulphur, selenium,tellurium etc., or a compound containing gold, platinum, palladium,iron, ruthenium, rhodium or iridium etc., a reducing agent such as a tinhalide etc., or a combination thereof. The details of these proceduresare described in T. H. James, "The Theory of the Photographic Process",Fourth Edition, Macmillan Publishing Co. Inc., New York (1977), Chapter5, pages 149 to 169.

Spectral Sensitizers

The recording material, according to the present invention, may containan infra-red sensitizer, an ultra-violet light sensitizer or a visiblelight sensitizer. Suitable sensitizers include cyanine, merocyanine,styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes. Usefulcyanine dyes include those having a basic nucleus, for example athiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, apyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazolenucleus and an imidazole nucleus. Preferred merocyanine dyes includethose having not only the above described basic nuclei but also acidnuclei, for example a thiohydantoin nucleus, a rhodanine nucleus, anoxazolidinedione nucleus, a thiazolidinedione nucleus, a barbituric acidnucleus, a thiazolinone nucleus, a malononitrile nucleus and apyrazolone nucleus. Of the above described cyanine and merocyanine dyes,those having imino groups or carboxyl groups are particularly preferred.

Suitable infra-red sensitizers include those disclosed in EP-A's 465078, 559 101, 616 014 and 635 756, JN's 03-080251, 03-163440, 05-019432,05-072662 and 06-003763 and U.S. Pat. Nos. 4,515,888, 4,639,414,4,713,316, 5,258,282 and 5,441,866.

Supersensitizers

According to the present invention the recording material furtherincludes a supersensitizer. Preferred supersensitzers are selected fromthe group of compounds consisting of: mercapto-compounds,disulfide-compounds, stilbene compounds, organoborate compounds andstyryl compounds. Suitable supersensitizers for use with infra-redspectral sensitizers are disclosed in EP-A 559 228, EP-A 587 338, U.S.Pat. No. 3,877,943, U.S. Pat. No. 4,873,184 and unpublished EuropeanPatent Application EP 96202107.7.

Antihalation Dyes

In addition to the ingredients, the recording materials used in thepresent invention may also contain antihalation or acutance dyes whichabsorb light which has passed through the photosensitive thermallydevelopable photographic material, thereby preventing its reflection.Such dyes may be incorporated into the photosensitive thermallydevelopable photographic material or in any other layer of thephotographic material of the present invention.

Antistatic Layer

In a preferred embodiment the recording material of the presentinvention an antistatic layer is applied to the outermost layer notcomprising at least one solid lubricant having a melting point below150° C. and at least one liquid lubricant in a binder, wherein at leastone of the lubricants is a phosphoric acid derivative.

Coating

The coating of any layer of the recording material of the presentinvention may proceed by any coating technique e.g. such as described inModern Coating and Drying Technology, edited by Edward D. Cohen andEdgar B. Gutoff, (1992) VCH Publishers Inc. 220 East 23rd Street, Suite909 New York, N.Y. 10010, U.S.A.

Thermographic Processing

Thermographic imaging is carried out by the image-wise application ofheat either in analogue fashion by direct exposure through an image ofby reflection from an image, or in digital fashion pixel by pixel eitherby using an infra-red heat source, for example with a Nd-YAG laser orother infra-red laser, with a thermographic material preferablycontaining an infra-red absorbing compound, or by direct thermal imagingwith a thermal head.

In thermal printing image signals are converted into electric pulses andthen through a driver circuit selectively transferred to a thermalprinthead. The thermal printhead consists of microscopic heat resistorelements, which convert the electrical energy into heat via Jouleeffect. The electric pulses thus converted into thermal signals manifestthemselves as heat transferred to the surface of the thermal paperwherein the chemical reaction resulting in colour development takesplace. Such thermal printing heads may be used in contact or closeproximity with the recording layer. The operating temperature of commonthermal printheads is in the range of 300 to 400° C. and the heatingtime per picture element (pixel) may be less than 1.0 ms, the pressurecontact of the thermal printhead with the recording material being e.g.200-500 g/cm² to ensure a good transfer of heat.

In order to avoid direct contact of the thermal printing heads with arecording layer not provided with an outermost protective layer, theimage-wise heating of the recording layer with the thermal printingheads may proceed through a contacting but removable resin sheet or webwherefrom during the heating no transfer of recording material can takeplace.

The image signals for modulating the laser beam or current in themicro-resistors of a thermal printhead are obtained directly e.g. fromopto-electronic scanning devices or from an intermediary storage means,e.g. magnetic disc or tape or optical disc storage medium, optionallylinked to a digital image work station wherein the image information canbe processed to satisfy particular needs.

Activation of the heating elements can be power-modulated orpulse-length modulated at constant power. The image-wise heating can becarried out such that heating elements not required to produce an imagepixel generate an amount of heat (H_(e)) in accordance with thefollowing formula:

    0.5 H.sub.D <H.sub.e <H.sub.D

wherein H_(D) represents the minimum amount of heat required to causevisible image formation in the thermographic recording material.

EP-A 654 355 describes a method for making an image by image-wiseheating by means of a thermal head having energizable heating elements,wherein the activation of the heating elements is executed duty cycledpulsewise. When used in thermographic recording operating with thermalprintheads the thermographic recording materials are not suitable forreproducing images with fairly large number of grey levels as isrequired for continuous tone reproduction. EP-A 622 217 discloses amethod for making an image using a direct thermal imaging elementproducing improvements in continuous tone reproduction.

Image-wise heating of the thermographic recording material can also becarried out using an electrically resistive ribbon incorporated into thematerial. Image- or pattern-wise heating of the thermographic recordingmaterial may also proceed by means of pixel-wise modulated ultra-sound,using e.g. an ultrasonic pixel printer as described e.g. in U.S. Pat.No. 4,908,631.

Photothermographic Processing

Photothermographic recording materials, according to the presentinvention, may be exposed with radiation of wavelength between an X-raywavelength and a 5 microns wavelength with the image either beingobtained by pixel-wise exposure with a finely focused light source, suchas a CRT light source; a UV, visible or IR wavelength laser, such as aHe/Ne-laser or an IR-laser diode, e.g. emitting at 780 nm, 830 nm or 850nm; or a light emitting diode, for example one emitting at 659 nm; or bydirect exposure to the object itself or an image therefrom withappropriate illumination e.g. with UV, visible or IR light.

For the thermal development of image-wise exposed photothermographicrecording materials, according to the present invention, any sort ofheat source can be used that enables the recording materials to beuniformly heated to the development temperature in a time acceptable forthe application concerned e.g. contact heating, radiative heating,microwave heating etc.

Industrial Application

Direct thermal imaging can be used for both the production oftransparencies and reflection type prints. Application of the presentinvention is envisaged in the fields of both graphics images requiringhigh contrast images with a very steep print density applied dot energydependence and continuous tone images requiring a weaker print densityapplied dot energy dependence, such as required in the medicaldiagnostic field. In the hard copy field recording materials on a whiteopaque base are used, whereas in the medical diagnostic fieldblack-imaged transparencies are widely used in inspection techniquesoperating with a light box.

While the present invention will hereinafter be described in connectionwith a preferred embodiment thereof, it will be understood that it isnot intended to limit the invention to that embodiment. On the contrary,it is intended to cover all alternatives, modifications, and equivalentsas may be included within the spirit and scope of the invention asdefined by the appending claims.

The invention is illustrated hereinafter by way of invention examplesand comparative examples. The percentages and ratios given in theseexamples are by weight unless otherwise indicated. The ingredients usedin the invention and comparative examples, other than those mentionedabove, are:

as organic silver salt:

AgB=silver behenate;

as binders:

PVB=BUTVAR™ B79, a polyvinyl butyral from Monsanto;

K7598=type K7598, a calcium-free gelatin from Koepff;

LATEX 01=a latex of a copolymer of 50% by weight of butadiene and 50% byweight of methyl methacrylate;

LATEX 02=a latex of a terpolymer of 47.5% by weight of butadiene, 47.5%by: weight of methyl methacrylate and 5% by weight of itaconic acid;

as reducing agents:

R01=ethyl 3,4-dihydroxybenzoate;

R02=3(3',4'-dihydroxyphenyl)propionic acid

as toning agents:

TA01=benzo[e][1,3]oxazine-2,4-dione;

TA02=7-(ethylcarbonato)-benzo[e][1,3]oxazine-2,4-dione (see formula IIbelow) ##STR1## TA03=succinimide; TA04=phthalazinone;

TA05=phthalazine;

as levelling agent:

oil=Baysilone™, a silicone oil from Bayer AG;

as stabilizers:

S01=tetrachlorophthalic anhydride;

S02=adipic acid;

S03=benzotriazole.

INVENTION EXAMPLES 1 to 7 and COMPARATIVE EXAMPLES 1 to 3

Preparation of Silver Behenate

The silver behenate types A to C of COMPARATIVE EXAMPLES 1 to 3 andsilver behenate types I to VII of INVENTION EXAMPLES 1 to 7 wereprepared by dissolving the required quantity of behenic acid in2-butanone at 60° C. with vigorous stirring followed by addingdemineralized water while maintaining the reactor at a temperature ofbetween 56 and 60° C., converting the behenic acid into sodium behenate,in the quantity and at the concentration specified in tables 1 and 2 forthe COMPARATIVE and INVENTION EXAMPLES respectively, by adding anaqueous solution of sodium hydroxide with vigorous stirring whilemaintaining the temperature of the reactor at a temperature between 56and 60° C. and finally converting the sodium behenate into silverbehenate by adding the quantity of silver nitrate specified for thespecific EXAMPLE and silver behenate type in tables 1 and 2 for theCOMPARATIVE and INVENTION EXAMPLES respectively as an aqueous solution,with the concentration specified for the specific EXAMPLE and silverbehenate type in tables 1 and 2 for the COMPARATIVE and INVENTIONEXAMPLES respectively, at the rate specified for the specific EXAMPLEand silver behenate type in tables 1 and 2 for the COMPARATIVE andINVENTION EXAMPLES respectively with vigorous stirring while maintainingthe reactor temperature at the temperature given for the specificEXAMPLE and silver behenate type in tables 1 and 2 for the COMPARATIVEand INVENTION EXAMPLES respectively. The final percentage by weight of2-butanone in the suspending mixture of 2-butanone and water and theinitial mixing number for the specific EXAMPLE and silver behenate typeare also given in tables 1 and 2 for the COMPARATIVE and INVENTIONEXAMPLES respectively.

                                      TABLE 1                                     __________________________________________________________________________             sodium behenate                                                                       silver nitrate                                                                        final     AgNO.sub.3                                                                        initial                                Comparative  concen- concen-                                                                           % by  tem-                                                                              addition                                                                          mixing                                 example                                                                             AgB                                                                              quantity                                                                          tration*                                                                          quantity                                                                          tration                                                                           weight                                                                              perature                                                                          time                                                                              number                                 number                                                                              type                                                                             [moles]                                                                           [M] [moles]                                                                           [M] 2-butanone                                                                          [° C.]                                                                     [min]                                                                             MN.sub.o                               __________________________________________________________________________    1     A  180 0.248                                                                             180 0.4 23    65  240 9.5 × 10.sup.-5                  2     B  180 0.248                                                                             180 0.4 23    65  240 9.5 × 10.sup.-5                  3     C  180 0.248                                                                             180 0.4 23    65  240 9.5 × 10.sup.-5                  __________________________________________________________________________     *initial concentration                                                   

                                      TABLE 2                                     __________________________________________________________________________            sodium behenate                                                                       silver nitrate                                                                        final     AgNO.sub.3                                                                          initial                               Invention   concen- concen-                                                                           % by  tem-                                                                              addition                                                                            mixing                                example                                                                            AgB                                                                              quantity                                                                          tration*                                                                          quantity                                                                          tration                                                                           weight                                                                              perature                                                                          time  number                                number                                                                             type                                                                             [moles]                                                                           [M] [moles]                                                                           [M] 2-butanone                                                                          [° C.]                                                                     [min] MN.sub.o                              __________________________________________________________________________    1    I  0.245                                                                             0.097                                                                             0.245                                                                             1.75                                                                              45    55  3.sup.+  + 55.sup.x                                                                 1.09 × 10.sup.-3                2    II 110.9                                                                             0.100                                                                             110.9                                                                             1.67                                                                              45    55  3.sup.+  + 15.sup.x                                                                 5.29 × 10.sup.-3                3    III                                                                              0.25                                                                              0.183                                                                             0.25                                                                              1.88                                                                              45    60  0.75  4.73 × 10.sup.-3                4    IV 151.4                                                                             0.194                                                                             151.4                                                                             5.91                                                                              45    55  1.5   1.60 × 10.sup.-2                5    V  0.5 0.158                                                                             0.5 3.76                                                                              45    55  1.5.sup.+  + 11.sup.x                                                               2.74 × 10.sup.-3                6    VI 98  0.087                                                                             98  5.91                                                                              45    55  1.08  2.92 × 10.sup.-2                7    VII                                                                              3.066                                                                             0.085                                                                             3.066                                                                             1.67                                                                              40    55  119   2.20 × 10.sup.-4                __________________________________________________________________________     *initial concentration                                                        .sup.+ first half of AgNO.sub.3                                               .sup.x second half of AgNO.sub.3                                         

INVENTION EXAMPLES 8 to 15 and COMPARATIVE EXAMPLES 4 to 6

Dispersions of Silver Behenate in 2-butanone

The dispersions of COMPARATIVE EXAMPLE 4, COMPARATIVE EXAMPLE 5 andINVENTION EXAMPLE 9 were obtained by ball milling for 120 hours 56.5 gof the dried silver behenate powders of COMPARATIVE EXAMPLE 1,COMPARATIVE EXAMPLE 2 and INVENTION EXAMPLE 1 respectively in a solutionof 56.5 g of PVB in 387.5 g of 2-butanone.

The dispersions of COMPARATIVE EXAMPLE 6 and INVENTION EXAMPLES 8 and 10to 15 were obtained by first preparing a predispersion of 56.5 g of thedried silver behenate powders of COMPARATIVE EXAMPLE 3 and INVENTIONEXAMPLES 1 to 7, as given below in tables 3 and 4, in a solution of 56.5g of PVB in 387.5 g of 2-butanone by stirring for 10 minutes with anUltra-Turrax™ stirrer. These predispersions were then microfluidized bypassing them once through a MICROFLUIDICS™ M-110Y high pressuremicrofluidizer at a jet pressure of 400 bar to produce the dispersionsof COMPARATIVE EXAMPLE 6 and INVENTION EXAMPLES 8 and 10 to 15.

Coating of Recording Materials

A subbed polyethylene terephthalate support having a thickness of 175 μmwas doctor blade-coated from a coating composition containing 2-butanoneas a solvent using the above-described silver behenate dispersions andthe additional ingredients given below so as to obtain thereon, afterdrying for 1 hour at 50° C., layers with the compositions given in table3 for COMPARATIVE EXAMPLES 4 to 6 with silver behenate types A to Crespectively, prepared according to COMPARATIVE EXAMPLES 1 to 3respectively, and table 4 for INVENTION EXAMPLES 8 to 15 with silverbehenate types I to VII as indicated therein, prepared according toINVENTION EXAMPLES 1 to 7.

Determination of the Crystallinity of Silver Behenate in the RecordingMaterials

The crystallinity of the silver behenate in the recording materials ofthe recording materials of COMPARATIVE EXAMPLES 4 to 6 and INVENTIONEXAMPLES 8 to 15 were determined as follows:

i) 30 mm diameter samples of the recording materials of COMPARATIVEEXAMPLES 4 to 6 and INVENTION EXAMPLES 8 to 15 and of NIST standard 1976were cut from larger sheets using a punch;

ii) X-ray diffraction scans were then carried out using a SIEMENS D5000X-ray diffractometer equipped with a copper Kα₁ X-ray source operatingat 40 keV and a current of 30 mA with the samples in the sample holderthereof to scan the samples of COMPARATIVE EXAMPLES 4 to 6, INVENTIONEXAMPLES 8 to 15 and NIST standard 1976, with the same X-raydiffractometer in exactly the same state of adjustment, in steps of 0.05degrees at a rate of 1 step/s between Bragg angles, 2Θ, of 5° and 50°and the data processed using SIEMENS DIFFRAC™ AT software to produceX-ray diffraction spectra corrected for background and exact peakheights of each X-ray diffraction peak. Five X-ray scans were carriedout for each sample, with the data being processed separately asdescribed above, and average peak heights calculated for each X-raydiffraction peak;

iii) the K_(material) values were then determined for the recordingmaterials of COMPARATIVE EXAMPLES 4 to 6 and INVENTION EXAMPLES 8 to 15by adding up the average peak heights of the X-ray diffraction linesattributable to silver behenate at Bragg angles, 2Θ, of 6.01°, 7.56°,9.12°, 10.66°, 12.12° and 13.62°;

iv) the K₁₉₇₆ value was determined for NIST standard 1976 by adding upthe average peak heights of the X-ray diffraction lines at Bragg angles,2Θ, of 25.60°, 35.16° and 43.40°;

v) the weights of silver, C_(Ag), present in 1 m² of the recordingmaterials of COMPARATIVE EXAMPLES 4 to 6 and INVENTION EXAMPLES 8 to 15were determined using a PHILIPS PW2400 wavelength dispersive X-rayfluorescence apparatus with a copper K.sub.α X-ray source operating at60 keV and a current of 50 mA, which had been calibrated for silverusing silver-containing samples for which the silver concentrations hadbeen determined using standard volumetric titration techniques; and

vi) the crystallinity values for the silver behenate present in therecording materials of COMPARATIVE EXAMPLES 4 to 6 and INVENTIONEXAMPLES 8 to 15 were determined using the expression: K_(material)/(K₁₉₇₆ ×C_(Ag)).

The crystallinity values for the silver behenate present in therecording materials of COMPARATIVE EXAMPLES 4 to 6 and INVENTIONEXAMPLES 8 to 15 are summarized in tables 3 and 4 respectively.

                                      TABLE 3                                     __________________________________________________________________________    Comparative                                                                   example                                                                             silver behenate                                                                            PVB R01 TA01                                                                              TA02                                                                              Oil S01 S02 S03                            nr    Type                                                                             Crystallinity                                                                       [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                   __________________________________________________________________________    4     A  0.71  5.426                                                                             21.70                                                                             1.111                                                                             0.297                                                                             0.152                                                                             0.048                                                                             0.173                                                                             0.390                                                                             0.144                          5     B  0.72  5.277                                                                             21.11                                                                             1.080                                                                             0.289                                                                             0.148                                                                             0.047                                                                             0.169                                                                             0.379                                                                             0.140                          6     C  0.65  5.953                                                                             23.81                                                                             1.218                                                                             0.326                                                                             0.167                                                                             0.053                                                                             0.191                                                                             0.427                                                                             0.158                          __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________    Invention                                                                     example                                                                            silver behenate                                                                            PVB R01 TA01                                                                              TA02                                                                              Oil S01 S02 S03                             nr   Type                                                                             Crystallinity                                                                       [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                    __________________________________________________________________________     8   I  1.57  4.978                                                                             19.91                                                                             1.019                                                                             0.272                                                                             0.140                                                                             0.045                                                                             0.159                                                                             0.357                                                                             0.133                            9   I  1.04  5.136                                                                             20.54                                                                             1.051                                                                             0.281                                                                             0.144                                                                             0.046                                                                             0.164                                                                             0.369                                                                             0.137                           10   II 1.54  5.031                                                                             20.12                                                                             1.030                                                                             0.275                                                                             0.141                                                                             0.045                                                                             0.161                                                                             0.361                                                                             0.134                           11   III                                                                              1.42  4.820                                                                             19.28                                                                             0.987                                                                             0.264                                                                             0.135                                                                             0.043                                                                             0.154                                                                             0.346                                                                             0.128                           12   IV 1.68  4.978                                                                             19.91                                                                             1.019                                                                             0.264                                                                             0.140                                                                             0.045                                                                             0.159                                                                             0.357                                                                             0.133                           13   V  1.68  4.899                                                                             19.60                                                                             1.003                                                                             0.268                                                                             0.138                                                                             0.044                                                                             0.157                                                                             0.352                                                                             0.130                           14   VI 1.00  4.820                                                                             19.28                                                                             0.987                                                                             0.264                                                                             0.135                                                                             0.043                                                                             0.154                                                                             0.346                                                                             0.128                           15   VII                                                                              1.58  5.479                                                                             21.92                                                                             1.121                                                                             0.300                                                                             0.154                                                                             0.049                                                                             0.175                                                                             0.447                                                                             0.146                           __________________________________________________________________________

Thermographic Printing

The printer was equipped with a thin film thermal head with a resolutionof 300 dpi and was operated with a line time of 19 ms (the line timebeing the time needed for printing one line). During the line time theprint head received constant power. The average printing power, beingthe total amount of electrical input energy during one line time dividedby the line time and by the surface area of the heat-generatingresistors was 1.5 mJ/dot being sufficient to obtain maximum opticaldensity in each of the recording materials. During printing the printhead was separated from the imaging layer by a thin intermediatematerial contacted with a slipping layer of a separable 5 μm thickpolyethylene terephthalate ribbon coated successively with a subbinglayer, heat-resistant layer and the slipping layer (anti-friction layer)giving the ribbon with a total thickness of 6 μm.

Image Evaluation

The optical maximum and minimum densities of the prints obtained withthe recording materials of COMPARATIVE EXAMPLES 4 to 6 and INVENTIONEXAMPLES 8 to 15 measured through a visual filter with a Macbeth™ TR924densitometer for grey scale steps corresponding to data levels of 255and 0 respectively are given in tables 5 and 6.

Image Tone Assessment

The image tone was determined by first printing recording materialswhich had been tempered for 7 days at 45° C. as described above and thensubjecting the prints to visual inspection and to measurement of the b*CIELAB-value of the image as a function of image density as determinedwith a MACBETH™ TR924 densitometer. The L*, a* and b* CIELAB-values weredetermined by spectrophotometric measurements according to ASTM NormE179-90 in a R(45/0) geometry with evaluation according to ASTM NormE308-90. The visually assessed image tone and the b* value at theminimum in the dependence of b* upon image density for the recordingmaterials of COMPARATIVE EXAMPLES 4 to 6 and INVENTION EXAMPLES 8 to 15are also summarized in tables 5 and 6 respectively.

                  TABLE 5                                                         ______________________________________                                        Comparative     print characteristics                                         example AgB                 image tone from                                                                         b* at minimum                           number  type    D.sub.max                                                                            D.sub.min                                                                          visual inspection                                                                       in b* vs OD                             ______________________________________                                        4       A       3.39   0.07 brown     -0.1                                    5       B       3.48   0.07 brown     -0.4                                    6       C       2.84   0.09 brown     -1.5                                    ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                        Invention      print characteristics                                          example                                                                              AgB                 image tone from                                                                          b* at minimum                           number type    D.sub.max                                                                            D.sub.min                                                                          visual inspection                                                                        in b* vs OD                             ______________________________________                                         8     I       3.21   0.07 blue       -4.3                                     9     I       2.82   0.07 blue       -3.4                                    10     II      3.13   0.07 blue/red   -4.8                                    11     III     2.81   0.07 blue       -4.0                                    12     IV      2.81   0.07 blue       -3.3                                    13     V       3.32   0.07 blue/red   -3.0                                    14     VI      2.57   0.07 blue       -3.7                                    15     VII     2.86   0.08 blue       -5.1                                    ______________________________________                                    

The recording materials of COMPARATIVE EXAMPLES 4 to 6 with silverbehenate types A to C all exhibited prints with a brown tone and a b*value at the minimum in the b* dependence upon image density of greaterthan -2.0, whereas the recording materials of INVENTION EXAMPLES 8 to 15with silver behenate types I to VII prepared according to the presentinvention exhibited prints with a blue or blue/red tone and a b* valueat the minimum in the b* dependence upon image density of less than-2.0.

COMPARATIVE EXAMPLES 7 & 8

The crystallinity and visual tone of silver behenate in samples ofTHERMALRES™ FILM type PR-PM-film lot number 04673456 a thermographicrecording material based on a silver behenate-reducing-agent system fromLABELON, COMPARATIVE EXAMPLE 7, and of DRYVIEW™ 39701 DVB (blue) lotnumber 021132-013-A-025 a photothermographic recording material based ona silver behenate-reducing agent system from IMATION, COMPARATIVEEXAMPLE 8, was determined as described for INVENTION EXAMPLES 8 to 15and COMPARATIVE EXAMPLES 4 to 6 and the results are summarized in table7. Visual inspection of the silver behenate in the case of DRYVIEW™39701 DVB (blue) is not possible due to the use of a blue support.

                  TABLE 7                                                         ______________________________________                                        Comparative                      image tone from                              Example number                                                                          Recording material                                                                         Crystallinity                                                                           visual inspection                            ______________________________________                                        7         THERMALRES ™                                                                            0.46      brown                                                  PR-PM-Film                                                          8         DRYVIEW ™ 0.50      not possible                                           39701 (blue)                                                        ______________________________________                                    

COMPARATIVE EXAMPLE 9

Thermographic Recording Material Incorporating Silver Behenate ProducedAccording to the Teaching of EP-A 754 969

A sodium behenate solution was prepared by first dissolving 34 kg ofbehenic acid in 340 L of 2-propanol at 65° C. and then adding withstirring a 0.25N solution of sodium hydroxide until a solution pH of 8.7was obtained. This required about 400 L of 0.25N NaOH. The concentrationof the resulting solution was then adjusted to a sodium behenateconcentration of 8.9% by weight and a concentration of 2-propanol in thesolvent mixture of 16.7% by volume, by a combination of evaporation anddilution.

The silver behenate synthesis was carried out at a constant UAg of 400mV as follows: to a stirred solution of 30 g of gelatin (type 7598 fromAGFA GELATINFABRIK vorm. KOEPFF & SOEHNE) in 750 mL of distilled waterat 72° C. in a double walled reactor, several drops of a 2.94M aqueoussolution of silver nitrate were added to adjust the UAg at the start ofthe reaction to 400 mV and then 374 mL of the sodium behenate solution,whose preparation is described above, at a temperature of 78° C. wasmetered into the reactor at a rate of 46.6 mL/min and simultaneously a2.94M aqueous solution of silver nitrate was metered into the reactor,its addition rate being controlled by the quantity of the silver nitratesolution necessary to maintain a UAg of 400±5 mV in the dispersingmedium in the reactor. Both the sodium behenate and silver nitratesolutions were added to the dispersing medium via small diameter tubespositioned just under the surface of the dispersing medium. By the endof the addition step 0.092 moles of sodium behenate and 0.101 moles ofsilver nitrate had been added. The mixture was then stirred for afurther 30 minutes. The resulting silver behenate dispersion contained3.13% by weight of silver behenate and 2.28% by weight of K7598.

0.032 g of TA03, 2 g of a 20% by weight aqueous dispersion of LATEX 01and tenside were added with stirring to 15 g of this silver behenatedispersion and the resulting dispersion diluted with demineralized waterto a weight of 18.8 g before coating at a temperature of 40° C., using adoctor blade coater with a slit-width of 120 μm, onto a subbed 100 μmthick polyester sheet and dried. The dried layer consisted of: ca. 3g/m² silver behenate, ca. 2.5 g/m² of LATEX 01, ca. 2.2 g/m² of K7598and ca. 0.2 g/m² of TA03.

The crystallinity of the silver behenate in the thermo-graphic materialwas determined as described for INVENTION EXAMPLES 8 to 15 andCOMPARATIVE EXAMPLES 4 to 6 to be 0.33.

INVENTION EXAMPLES 16 to 20

Preparation of Silver Behenate Dispersions in an Aqueous Medium in theAbsence of Organic Solvent Using a Single Jet Process

Aqueous dispersions of the silver behenate types VIII to XII ofINVENTION EXAMPLES 16 to 20 were produced as follows:

i) dispersing 102.18 g (0.3M) behenic acid with stirring at 400 rpm witha 100 mm diameter typhoon stirrer in a 250 mm in diameter vessel at 80°C. in a quantity of mL of a 10% solution of Surfactant nr 1/g behenicacid (see table 8) made up to 1 L with deionized water at a temperatureof 80° C.;

ii) then adding 150 mL of a 2M aqueous solution of sodium hydroxide withstirring at 400 rpm with a 100 mm diameter typhoon stirrer to the 250 mmin diameter vessel at 80° C. over a period of 10 to 20 minutes to clearsolution substantially containing sodium behenate;

iii) then adding a 300 mL of a 1M (or 100 mL of 3M in cases of INVENTIONEXAMPLES 17 & 18) aqueous solution of silver nitrate with stirring at400 rpm with a 100 mm diameter typhoon stirrer to the 250 mm in diametervessel at a temperature of 80° C. at a particular rate of moles/molessilver behenate.min (see table 8 for the value for the particular silverbehenate type), to convert the sodium behenate completely into silverbehenate; and

iv) ultrafiltration with a 500000 MW polysulfone cartridge filter atroom temperature cassette to concentrate the resulting silver behenatedispersion (final AgB-concentration and residual conductivity in mS/cmare given in table 8).

The volume average particle size as determined by a Coulter LS230diffractometer is also given in table 8.

                                      TABLE 8                                     __________________________________________________________________________                                ultrafiltration                                                                          average                                Invention                                                                             Surfactant                                                                              Tem-                                                                              mol   residual   particle                               example                                                                            AgB   mL 10% sol./                                                                         perature                                                                          AgNO.sub.3 /mol                                                                     conductivity                                                                        % AgB                                                                              size                                   number                                                                             type                                                                             type                                                                             g HBeh [° C.]                                                                     AgB · min                                                                  [mS/cm]                                                                             dispersion                                                                         [μm]                                __________________________________________________________________________    16   VIII                                                                             nr 1                                                                             2.28   80  0.0625                                                                              4.9   23.3 0.433                                  17   IX nr 1                                                                             2.28   80  0.0625                                                                              4.3   18.9                                        18   X  nr 1                                                                             2.28   80  2.25        14.11                                                                              0.111                                  19   XI nr 1                                                                             4.56   80  0.0625                                                                              6.2   14.0 0.187                                  20   XII                                                                              nr 1                                                                             4.56   80  0.157 6.5   14.0 0.135                                  __________________________________________________________________________

These dispersions of silver behenate were directly used in thepreparation of thermographic recording materials comprisingthermographic elements coated from aqueous media.

Toning Agent Dispersions

toner dispersion 01: dispersion of TA01 in an aqueous solution ofSurfactant Nr 1 containing 30% of TA01 and 3% of Surfactant Nr. 1 (addedas a dispersion);

toner dispersion 02: dispersion of TA02 in a gelatin solution containing20% of K7598 (gelatin) and 10% of TA02 (added as flakes).

Preparation of Thermographic Recording Materials with the Aqueous SilverBehenate-Dispersions

The thermographic recording materials of INVENTION EXAMPLES 16 to 20were prepared by first dissolving K7598 in deionized water at 36° C.(see table 9 for quantities), then adding the appropriate Surfactant nr1-containing silver behenate emulsion (see table 9 for quantity andconcentration), then an aqueous dispersion of LATEX 02 with a pH of 5.0(for quantity see table 9) followed by 5 minutes stirring, then anaqueous toner dispersion (for number and quantity, see table 9), whilekeeping the dispersion at 36° C. followed by vigorous stirring, then 6.3g of toner dispersion 02 (see INVENTION EXAMPLES 16 to 20), then 11.23 gof a 13.7% by weight solution of R01 in ethanol and finally 1.31 g of a3.66% by weight aqueous solution of formaldehyde.

                  TABLE 9                                                         ______________________________________                                        Invention          AgB disp. Polymer 1                                                                             toner disp.                              example                                                                              water   K7598   conc wt.  conc wt.       wt.                           number [g]     [g]     [%]  [g]  [%]  [g]  nr   [g]                           ______________________________________                                        16     22.66   2.25    23.25                                                                              19.36                                                                              30   5.58 01   3.61                          17     10.58   2.26    18.9 23.68                                                                              30   5.57 02   5.38                          18     10.12   2.25    14.11                                                                              31.90                                                                              30   5.58 01   3.61                          19     9.90    2.25    14.0 32.13                                                                              30   5.58 01   3.61                          20     9.82    2.25    14.0 32.20                                                                              30   5.58 01   3.61                          ______________________________________                                    

The resulting silver behenate emulsions were then doctor blade-coatedonto a 175 μm thick subbed polyethylene terephthalate support to producethe coating weights of silver given in table 10.

The crystallinity of the silver behenate in the thermographic recordingmaterials of INVENTION EXAMPLES 16 to 20 were determined as describedfor INVENTION EXAMPLES 8 to 15 and COMPARATIVE EXAMPLES 4 to 6 and aregiven in table 10.

The thermographic recording materials of INVENTION EXAMPLES 16 to 20 andCOMPARATIVE EXAMPLE 7 were printed and the prints evaluated as describedfor INVENTION EXAMPLES 8 to 15 and COMPARATIVE EXAMPLES 4 to 6. Themaximum and minimum densities of the prints obtained with thethermographic recording materials of INVENTION EXAMPLES 16 to 20measured through a blue filter with a Macbeth™ TR924 densitometer forgrey scale steps corresponding to data levels of 255 and 0 respectivelyare also given in table 10.

Archivability Test

The achivability of prints made with the thermographic recordingmaterials of INVENTION EXAMPLES 16 to 20 and COMPARATIVE EXAMPLE 7 wasevaluated on the basis of the observed changes in minimum density uponheating the prints at 57° C. in a relative humidity (RH) of 34% for 3days in the dark. The results of these tests are given in table 10.

Light Box Test

The stability of the image background of the prints made with thethermographic recording materials of INVENTION EXAMPLES 16 to 20 andCOMPARATIVE EXAMPLE 7 was evaluated on the basis of the change inminimum (background) density measured through a blue filter using aMacBeth™ TR924 densitometer upon exposure on top of the white PVC windowof a specially constructed light-box placed for 3 days in a Votschconditioning cupboard set at 30° C. and a relative humidity (RH) of 85%.Only a central area of the window 550 mm long by 500 mm wide was usedfor mounting the test materials to ensure uniform exposure.

The stainless steel light-box used was 650 mm long, 600 mm wide and 120mm high with an opening 610 mm long and 560 mm wide with a rim 10 mmwide and 5 mm deep round the opening, thereby forming a platform for a 5mm thick plate of white PVC 630 mm long and 580 mm wide, making thewhite PVC-plate flush with the top of the light-box and preventing lightloss from the light-box other than through the white PVC-plate. Thislight-box was fitted with 9 Planilux TLD 36 W/54 fluorescent lamps 27 mmin diameter mounted length-wise equidistantly from the two sides, withthe lamps positioned equidistantly to one another and the sides over thewhole width of the light-box and with the tops of the fluorescent tubes30 mm below the bottom of the white PVC plate and 35 mm below thematerials being tested.

The results of the light box tests are also given in table 10. Thesilver behenate in the thermographic recording materials of INVENTIONEXAMPLES 16 to 20 exhibit high to very high crystallinities, accordingto the present invention, and the thermographic recording materials withthese silver behenate particles with high to very high crystallinityexhibit minimum densities which are hardly changed upon being subjectedto archivability and light box tests the present invention.

                                      TABLE 10                                    __________________________________________________________________________    Silver behenate    fresh print                                                                           ΔD.sub.min (blue)                                                             ΔD.sub.min (blue)                               coating   characteristics                                                                       archivability                                                                       light box                                             weight    D.sub.max                                                                         D.sub.min                                                                         (3d/57° C./                                                                  (3d/30° C./                           type     [g/m.sup.2 ]                                                                      crystallinity                                                                       (blue)                                                                            (blue)                                                                            34% RH)                                                                             85% RH)                                      __________________________________________________________________________    Comparative  0.46  >4.0                                                                              0.10                                                                              +0.83 +0.02                                        example                                                                       number                                                                        Invention                                                                     example                                                                       number                                                                        16    VIII                                                                             2.86                                                                              5.39  4.41                                                                              0.14                                                                              -0.01 0.03                                         17    IX 3.98                                                                              1.76  3.56                                                                              0.11                                                                              +0.01 0.04                                         18    X  3.61                                                                              3.20  3.27                                                                              0.12                                                                              -0.03 -0.01                                        19    XI 3.82                                                                              7.30  3.02                                                                              0.11                                                                              -0.01 0.00                                         20    XII                                                                              4.19                                                                              1.92  3.16                                                                              0.13                                                                              -0.02 -0.01                                        __________________________________________________________________________

INVENTION EXAMPLE 21

The photothermographic recording material of INVENTION EXAMPLE 21produced using a silver behenate dispersion prepared by first preparinga predispersion by adding 56.5 g of the dried silver behenate powdertype II of INVENTION EXAMPLE 2 to a solution of 56.5 g of PVB in 413.1 gof 2-butanone and then stirring for 10 minutes with an Ultra-Turrax™stirrer. This predispersion was then microfluidized by passing it oncethrough a MICROFLUIDICS™ M-110Y pressure microfluidizer at a jetpressure of 400 bar to produce 74% by weight dispersion of silverbehenate in 2-butanone.

A photothermographic coating dispersion was then obtained by mixing43.326 g of the silver behenate dispersion with 48.959 g of a 30% byweight solution of PVB for 20 minutes, 0.145 g of potassium iodidefollowed by 15 minutes stirring, 0.934 g of a 2-butanone solutioncontaining 30% by weight of TA01 and 15.4% by weight of TA02 followed by20 minutes stirring, 0.441 g of a 10% by weight solution of Oil in2-butanone followed by 20 minutes stirring and 0.351 g of S02 followedby 20 minutes stirring. To this dispersion was then added with stirringa solution of 0.997 g of R01, 0.078 g of S01 and 0.130 g of S03. Theresulting coating dispersion was then doctor blade-coated to a wetthickness of 120 μm onto a subbed polyethylene terephthalate supporthaving a thickness of 175 μm to obtain, after drying for 1 hour at 50°C., a photothermographic recording material with a silver behenatecoating weight of 4.31 g/m² and a silver iodide coating weight of 0.19g/m².

The crystallinity of the silver behenate in the photothermographicrecording materials of INVENTION EXAMPLE 21 was determined as describedfor INVENTION EXAMPLES 8 to 15 and COMPARATIVE EXAMPLES 4 to 6 to be1.16.

The photothermographic recording material INVENTION EXAMPLE 21 was thenexposed to ultra-violet light through a test original in contact withthe material in an Agfa-Gevaert™ DL 1000 exposure apparatus followed byheating on a heated metal block for 5 s at 100° C. to produce a goodimage.

INVENTION EXAMPLE 22

The photothermographic recording material of INVENTION EXAMPLE 22 wasproduced using a silver behenate dispersion prepared as described inINVENTION EXAMPLE 20 for silver behenate type XII except that noultrafiltration was carried out and that the concentration of silverbehenate in the dispersion was 8.15% by weight instead of 14.0% byweight.

A photothermographic coating dispersion was then obtained by mixing withstirring 7.5 g of the silver behenate dispersion with 4 g of an 0.44% byweight aqueous solution of potassium iodide, then 2 g of a 20% by weightaqueous dispersion of LATEX 02, then 0.64 g of a 5.6% by weight aqueoussolution of phthalazine and finally with 2 g of a 5.6% by weight aqueoussolution of R02. The resulting coating dispersion was then doctorblade-coated to a wet thickness of 120 μm onto a subbed polyethyleneterephthalate support having a thickness of 100 μm to obtain, afterdrying for 1 hour at 50° C., a photothermographic recording materialwith a silver behenate coating weight of 3.28 g/m² and a silver iodidecoating weight of 0.12 g/m².

The crystallinity of the silver behenate in the photothermographicrecording materials of INVENTION EXAMPLE 23 was determined as describedfor INVENTION EXAMPLES 8 to 15 and COMPARATIVE EXAMPLES 4 to 6 to be1.10.

The photothermographic recording material of INVENTION EXAMPLE 22 wasthen exposed to ultra-violet light through a test original in contactwith the material in an Agfa-Gevaer™ DL 1000 exposure apparatus followedby heating on a heated metal block for 5 s at 100° C. to produce a verygood image with a high contrast.

INVENTION EXAMPLE 23

The photothermographic recording material of INVENTION EXAMPLE 23 wasproduced using the silver behenate dispersion described in INVENTIONEXAMPLE 22. A photothermographic coating dispersion was then obtained asdescribed for INVENTION EXAMPLE 22 except that 4 g of 0.97% by weightaqueous solution of calcium iodide was used instead of 4 g of an 0.44%by weight aqueous solution of potassium iodide. The resulting coatingdispersion was then doctor blade-coated to a wet thickness of 120 μmonto a subbed polyethylene terephthalate support having a thickness of100 μm to obtain, after drying for 1 hour at 50° C., aphotothermographic recording material with a silver behenate coatingweight of 3.17 g/m² and a silver iodide coating weight of 0.11 g/m².

The crystallinity of the silver behenate in the photothermographicrecording materials of INVENTION EXAMPLE 23 was determined as describedfor INVENTION EXAMPLES 8 to 15 and COMPARATIVE EXAMPLES 4 to 6 to be1.22.

The photothermographic recording material INVENTION EXAMPLE 23 was thenexposed and thermally developed as described above for INVENTION EXAMPLE22 to produce a very good image with a high contrast.

INVENTION EXAMPLES 24 to 26

Enhancement of Silver Behenate Crystallinity in the Presence ofPhosphonium Compounds

The thermographic recording materials of INVENTION EXAMPLES 24 to 26 hada composition which differed from that of INVENTION EXAMPLE 10.Therefore, since the composition has an influence upon the image colour,the print characteristics of INVENTION EXAMPLES 24 to 26 are notdirectly comparable with that of INVENTION EXAMPLE 10.

The thermographic recording materials of INVENTION EXAMPLES 24 to 26were produced using a silver behenate dispersion prepared by firstpreparing a predispersion by adding 56.5 g of the dried silver behenatepowder type II of INVENTION EXAMPLE 2 to a solution of 56.5 g of PVB in413.1 g of 2-butanone and then stirring for 10 minutes with anUltra-Turrax™ stirrer. This predispersion was then microfluidized bypassing it once through a MICROFLUIDICS™ M-110Y high pressuremicrofluidizer at a jet pressure of 400 bar to produce a 10.74% byweight dispersion of silver behenate in 2-butanone.

Coating of Recording Materials

A subbed polyethylene terephthalate support having a thickness of 175 μmwas doctor blade-coated from a coating composition containing 2-butanoneas a solvent using the above-described silver behenate dispersions andthe additional ingredients given below so as to obtain thereon, afterdrying for 1 hour at 50° C., layers with the compositions given in Table11 for the thermographic recording materials of INVENTION EXAMPLES 24 to26.

                                      TABLE 11                                    __________________________________________________________________________    Invention                                                                          silver behenate Phosphonium                                              example                                                                            Crystal-                                                                              PVB R01 compound                                                                             TA01                                                                              TA02                                                                              Oil S01 S02 S03                           nr   linity                                                                            [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      type                                                                             [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                  __________________________________________________________________________    24   1.62                                                                              5.27                                                                              21.1                                                                              1.07                                                                              -- --  0.32                                                                              0.16                                                                              0.047                                                                             0.08                                                                              0.38                                                                              0.14                          25   2.25                                                                              4.56                                                                              18.3                                                                              0.93                                                                              PC01                                                                             0.40                                                                              0.28                                                                              0.14                                                                              0.041                                                                             0.07                                                                              0.33                                                                              0.12                          26   2.57                                                                              4.60                                                                              18.4                                                                              0.94                                                                              PC02                                                                             0.38                                                                              0.28                                                                              0.14                                                                              0.041                                                                             0.07                                                                              0.33                                                                              0.12                          __________________________________________________________________________

The crystallinity values for the silver behenate present in thethermographic recording materials of INVENTION EXAMPLES 24 to 26determined as described for COMPARATIVE EXAMPLES 4 to 6 and INVENTIONEXAMPLES 8 to 15 are summarized in Table 12. It is clear from theseresults that the presence of the phosphonium compounds PC01 and PC02 hasincreased the crystallinity of the silver behenate in the recordingmaterials of INVENTION EXAMPLES 25 & 26 over that of the silver behenatein the thermographic recording material of INVENTION EXAMPLE 24 with thesame concentrations of the other ingredients.

Thermographic printing with the thermographic recording materials ofINVENTION EXAMPLES 24 to 26 and the evaluation thereof were carried outas described for the thermographic recording materials of COMPARATIVEEXAMPLES 4 to 6 and INVENTION EXAMPLES 8 to 15. The evaluation resultsare summarized in Table 12.

                  TABLE 12                                                        ______________________________________                                                      print characteristics                                           Invention                                                                            AgB     Phos-              image tone                                                                            b* at min-                          example                                                                              crystal-                                                                              phonium            from visual                                                                           imum in                             number linity  compound D.sub.max                                                                          D.sub.min                                                                          inspection                                                                            b* vs OD                            ______________________________________                                        24     1.62    --       3.87 0.08         -0.9                                25     2.25    PC01     2.84 0.07 blue    -3.3                                26     2.57    PC02     3.10 0.06 blue    -2.4                                ______________________________________                                    

For the thermographic recording materials of INVENTION EXAMPLES 24 to 26with the same composition, the increase in crystallinity upon additionof the phosphonium compounds at a concentration of 8 mol % with respectto the silver behenate present brought about a, desirable for imagetone, reduction in the b.-value at the minimum in b. versus ODcharacteristic.

INVENTION EXAMPLES 27 to 31

The thermographic recording materials of INVENTION EXAMPLES 27 to 31were prepared using a silver behenate powder type XIII produced asdescribed for INVENTION EXAMPLE 4 except that the addition time was 2.5minutes instead of 1.5 minutes and the final % by weight of 2-butanonewas 40.9 instead of 45. A silver behenate was prepared with the type XIVsilver behenate powder by first preparing a predispersion by adding 56.5g of the dried silver behenate powder type XIII to a solution of 56.5 gof PVB in 389.2 g of 2-butanone and stirring for 10 minutes with anUltra-Turrax™ stirrer. This predispersion was then microfluidized bypassing it once through a MICROFLUIDICS™ M-110Y high pressuremicrofluidizer at a jet pressure of 400 bar to produce a 11.25% byweight dispersion of silver behenate in 2-butanone.

A subbed polyethylene terephthalate support having a thickness of 175 μmwas doctor blade-coated from a coating composition containing 2-butanoneas a solvent using the above-described silver behenate dispersions andthe additional ingredients given below so as to obtain thereon, afterdrying for 1 hour at 50° C., layers with the compositions given in Table13 for the thermographic recording materials of INVENTION EXAMPLES 27 to31.

The crystallinity values for the silver behenate present in thethermographic recording materials of INVENTION EXAMPLES 27 to 31determined as described for COMPARATIVE EXAMPLES 4 to 6 and INVENTIONEXAMPLES 8 to 15 are also summarized in Table 13.

                                      TABLE 13                                    __________________________________________________________________________    Invention                                                                          silver behenate PC01                                                     example                                                                            Crystal-                                                                              PVB R01 mol %   TA01                                                                              TA02                                                                              Oil S01 S02 S03                          nr   linity                                                                            [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      vs AgB                                                                            [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                                                                      [g/m.sup.2 ]                 __________________________________________________________________________    27   1.52                                                                              3.90                                                                              15.6                                                                              0.79                                                                              0   0   0.24                                                                              0.12                                                                              0.035                                                                             0.062                                                                             0.28                                                                              0.10                         28   1.78                                                                              4.07                                                                              16.3                                                                              0.83                                                                              2   0.09                                                                              0.25                                                                              0.13                                                                              0.037                                                                             0.065                                                                             0.29                                                                              0.11                         29   1.86                                                                              3.90                                                                              15.6                                                                              0.79                                                                              4   0.17                                                                              0.24                                                                              0.12                                                                              0.035                                                                             0.062                                                                             0.28                                                                              0.10                         30   1.82                                                                              3.94                                                                              15.8                                                                              0.80                                                                              6   0.26                                                                              0.24                                                                              0.12                                                                              0.035                                                                             0.063                                                                             0.28                                                                              0.10                         31   1.64                                                                              4.27                                                                              17.1                                                                              0.87                                                                              8   0.38                                                                              0.26                                                                              0.13                                                                              0.038                                                                             0.068                                                                             0.31                                                                              0.11                         __________________________________________________________________________

It is evident from table 13 that the crystallinities of the silverbehenate in the thermographic recording materials of INVENTION EXAMPLES28 to 31 in which the phosphonium compound PC01 is present are higherthan that of the silver behenate in the thermographic recording materialof INVENTION EXAMPLE 27 and moreover that there is an increase in silverbehenate crystallinity with increasing PC01-concentration up to aconcentration of 4 to 6 mol % with respect to the silver behenatepresent.

Thermographic printing with the thermographic recording materials ofINVENTION EXAMPLES 27 to 31 and the evaluation thereof were carried outas described for the thermographic recording materials of COMPARATIVEEXAMPLES 4 to 6 and INVENTION EXAMPLES 8 to 15. The evaluation resultsare summarized in Table 14.

                  TABLE 14                                                        ______________________________________                                                     print characteristics                                            Invention                                                                            AgB     mol %             image tone                                                                            b* at                                example                                                                              crystal-                                                                              PC01              from visual                                                                           minimum in                           number linity  vs AgB  D.sub.max                                                                          D.sub.min                                                                          inspection                                                                            b* vs OD                             ______________________________________                                        27     1.52    0       2.50 0.06 blue    -5.1                                 28     1.78    2       2.54 0.06 blue    -4.25                                29     1.86    4       2.66 0.07 blue    -4.55                                30     1.83    6       2.65 0.07 blue    -4.7                                 31     1.64    8       2.94 0.07 blue    -3.8                                 ______________________________________                                    

The results of table 14 for thermographic recording materials ofINVENTION EXAMPLES 28 to 31 with the phosphonium compound PC01 indifferent concentrations show comparable b.sup.· -values at the minimumin b.sup.· versus OD characteristics to the thermographic recordingmaterial of INVENTION EXAMPLE 27 without a phosphonium compound.

Having described in detail preferred embodiments of the currentinvention, it will now be apparent to those skilled in the art thatnumerous modifications can be made therein without departing from thescope of the invention as defined in the following claims.

What is claimed is:
 1. A process for producing particles of asubstantially light-insensitive organic silver salt, said particlescontaining silver behenate, said process comprising:(i) preparing asolution or dispersion, A, containing an alkali metal or ammonium saltof an organic compound with at least one acidic hydrogen atom, saidorganic compound including behenic acid, said salt of the organiccompound containing alkali or ammonium ions, in a mixture of water andan organic solvent, at a temperature at which particles of saidsubstantially light-insensitive organic silver salt containing silverbehenate do not undergo reduction; and (ii) adding a quantity of anaqueous solution, B, of a silver salt containing an equal number ofsilver ions to the alkali or ammonium ions in said solution ordispersion A; wherein an initial mixing number during said addition ofsaid aqueous solution B to said solution or dispersion A is greater thanor equal to 2×10⁻⁴ during said production of said particles ofsubstantially light-insensitive organic silver salt containing silverbehenate, said mixing number being defined as the ratio of the molarrate at which said silver salt is supplied to said solution ordispersion A in a reactor to the molar rate at which said alkali orammonium salt of the organic compound is circulated in said reactor; andwherein said particles of the substantially light-insensitive organicsilver salt, said particles containing silver behenate, are notassociated with mercury and/or lead ions.
 2. The process according toclaim 1, wherein concentration of said alkali or ammonium salt in saidsolution or dispersion A is greater than 0.022 moles/L.
 3. The processaccording to claim 1, wherein the organic solvent is present at between20 and 80% by weight of said mixture of water and an organic solvent. 4.The process according to claim 1, wherein the organic solvent is presentat between 35 and 65% by weight of said mixture of water and an organicsolvent.
 5. The process according to claim 1, wherein said solvent is2-butanone.
 6. The process according to claim 1, wherein at least 20% byweight of said particles are present as globular particles.
 7. Theprocess according to claim 1, wherein at least 40% by weight of saidparticles are present as globular particles.
 8. A recording material,comprising:a support; a thermosensitive element containing particles ofsubstantially light-insensitive organic silver salt, said particlescontaining silver behenate, produced by a process comprising:(i)preparing a solution or dispersion, A, comprising an alkali metal orammonium salt of an organic compound, said organic compound includingbehenic acid, said salt of the organic compound containing alkali orammonium ions, in a mixture of water and an organic solvent at atemperature at which particles of said substantially light-insensitiveorganic silver salt containing silver behenate do not undergo reduction;and (ii) adding a quantity of an aqueous solution, B, of a silver saltcontaining an equal number of silver ions to the alkali or ammonium ionsin said solution or dispersion A;wherein an initial mixing number duringsaid addition of said aqueous solution B to said solution or dispersionA is greater than or equal to 2×10⁻⁴ during said production of saidparticles of substantially light-insensitive organic silver saltcontaining silver behenate, said mixing number being defined as a ratioof the molar rate at which said silver salt is supplied to said solutionor dispersion A in a reactor to the molar rate at which said alkali orammonium salt is circulated in said reactor; an organic reducing agenttherefor in thermal working relationship therewith; and a binder;whereinsaid particles of substantially light-insensitive organic silver saltcontaining silver behenate are not associated with mercury and/or leadions, and wherein crystallinity of said silver behenate is greater than1.20, said crystallinity being defined as a ratio of a sum of peakheights of X-ray diffraction lines attributable to silver behenate atBragg angles, 2Θ, of 6.01°, 7.56°, 9.12°, 10.66°, 12.12° and 13.62° to asum of peak heights of X-ray diffraction lines of NIST standard 1976,rhombohedral Al₂ O₃, at Bragg angles, 2Θ, of 25.60°, 35.16° and 43.40°,being determined by irradiating the recording material with a copper Kα₁source with the same X-ray diffractometer in the same state ofadjustment, and normalized to a quantity of silver of 1 gram per m² ofthe recording material.
 9. The recording material according to claim 8,wherein said thermosensitive element further contains a toning agent.10. The recording material according to claim 8, wherein saidthermosensitive element is provided with a protective layer.
 11. Therecording material according to claim 8, wherein said thermosensitiveelement further contains a photosensitive species capable upon exposureof forming a species capable of catalyzing reduction of said silverbehenate.
 12. A recording process, comprising:(A) bringing an outermostlayer of a recording material into proximity with a heat source, saidrecording material includinga support; a thermosensitive element,containing particles of substantially light-insensitive organic silversalt, said particles containing silver behenate, said thermosensitiveelement produced by a process comprising:(i) preparing a solution ordispersion, A, containing an alkali metal or ammonium salt of an organiccompound with at least one acidic hydrogen atom, said organic compoundincluding behenic acid, said salt of the organic compound containingalkali or ammonium ions, in a mixture of water and an organic solvent ata temperature at which particles of said substantially light-insensitiveorganic silver salt containing silver behenate do not undergo reduction;and (ii) adding a quantity of an aqueous solution, B, of a silver saltcontaining an equal number of silver ions to the alkali or ammonium ionsin said solution or dispersion A;wherein an initial mixing number duringsaid addition of said aqueous solution B to said solution or dispersionA is greater than or equal to 2×10⁻⁴ during said production of saidparticles of substantially light-insensitive organic silver saltcontaining silver behenate, said mixing number being defined as a ratioof the molar rate at which said silver salt is supplied to said solutionor dispersion A in a reactor to the molar rate at which said alkali orammonium salt is circulated in said reactor; an organic reducing agenttherefor in thermal working relationship therewith; and a binder; (B)applying heat from said heat source by imagewise heating of therecording material while maintaining proximity to said heat source toproduce an image; and (C) removing said recording material from saidheat source;wherein said particles are not associated with mercuryand/or lead ions.
 13. The recording process according to claim 12,wherein said heat source is a thin film thermal head.